The PPO films with ordered structures have many potential applications in electronics, optics, separation, etc. Its self-supporting film with regular pores is prepared by evaporating the polyphenylene oxide (PPO) solution in carbon bisulfide under humid ambience. It is demonstrated that the nucleation, growth and ordered packing of water droplets condensed on the PPO solution layer as templates in the process are crutial for high-quality honeycomb films. The humidity, concentration, spreading volume of the PPO solution and the direction of airflow have great impact on the pore size, regularity of the film and so on, which are clarified by experiments.